Catalyst-Free Reaction of Ethynyl-π-Extended Electron Acceptors with Amines

Transcription

1 Catalyst-Free Reaction of Ethynyl-π-Extended Electron Acceptors with Amines Atsuro Takai* and Masayuki Takeuchi* 2018 The Chemical Society of Japan

2 Table of Contents S1. Synthesis and Characterization Page S2 S2. NMR Data Page S5 S3. Supporting Data (Figures S1 S12, Tables S1 S3) Page S10 S4. References Page S32 S1

3 S1. Synthesis and Characterization C 8 H 17 N N C 8 H 17 TMS C 8 H 17 N N C 8 H 17 CuI, Pd II cat. THF, DIPA Br NDI-Br 1 NDI1-pre NDI1-pre was synthesized according to the literature. Characterization data are in accordance with published data. 1 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.38 (s, 9H), 0.88 (m, 6H), (m, 20H), 1.74 (h, J = 8.2 Hz, 4H), 4.18 (td, J = 7.8, 1.9 Hz, 4H), 8.72 (d, J = 7.6 Hz, 1H), 8.77 (d, J = 7.6 Hz, 1H), 8.78 (s, 1H). 13 C NMR (101 MHz, CDCl 3 ): δ (ppm) = 0.14, 14.24, 14.25, 22.78, 22.80, 27.20, 27.24, 28.10, 28.18, 29.32, 29.35, 29.41, 29.42, 31.94, 31.97, 41.15, 41.19, , , , , , , , , , , , , , , , TMS C 8 H 17 N N C 8 H 17 KF THF, H 2 C 8 H 17 N N C 8 H 17 NDI1-pre TMS NDI1 To a Schlenk flask containing NDI1-pre (60 mg, 0.10 mmol) was added 2 ml of dry THF under Ar atmosphere. An aqueous solution (0.5 ml) of potassium fluoride (KF, 89 mg, 1.53 mmol) was purged with Ar and added into the flask. The biphasic mixture was stirred vigorously for 5 h at 308 K (35 C), after which the product was extracted with CH 2 Cl 2. The organic phase was dried over NaS 4, evaporated, and purified by silica gel column chromatography (CHCl 3 ) to yield a yellow solid. The solid was further purified by gel permeation chromatography and reprecipitation from CH 2 Cl 2 and MeH to afford a light yellow solid (36 mg, 69%). 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.87 (m, 6H), (m, 20H), 1.74 (m, 4H), 4.01 (s, 1H), 4.19 (m, 4H), 8.75 (d, J = 7.6 Hz, 1H), 8.81 (d, J = 7.6 Hz, 1H), 8.82 (s, 1H). 13 C NMR (101 MHz, CDCl 3 ): δ (ppm) = 14.24, 22.78, 27.21, 27.30, 28.18, 28.19, 29.33, 29.36, 29.42, 29.45, 31.95, 41.22, 41.43, 82.33, 90.18, , , , , , , , , , , , , , Elemental analysis (calcd for C 32 H 38 N 2 4 : C, 74.68; H, 7.44; N, 5.44): found C, 74.76; H, 7.39; N, S2

4 TMS C 8 H 17 N N C 8 H 17 KF THF, H 2 C 8 H 17 N N C 8 H 17 NDI2-pre TMS NDI2 Compound NDI2 was synthesized from NDI2-pre according to the above-described procedure for NDI1. Yellow solid (78%); 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.87 (m, 6H), (m, 20H), 1.74 (p, J = 7.5 Hz, 4H), 4.04 (s, 2H), 4.19 (m, 4H), 8.86 (s, 2H). 13 C NMR (101 MHz, CDCl 3 ): δ (ppm) = 14.24, 22.78, 27.27, 28.13, 29.35, 29.43, 31.94, 41.48, 82.21, 90.74, , , , , , , Elemental analysis (calcd for C 34 H 38 N 2 4 : C, 75.81; H, 7.11; N, 5.20): found C, 76.02; H, 7.16; N, TMS C 12 H 25 N N C 12 H 25 K 2 C 3 MeH, MCH C 12 H 25 N N C 12 H 25 PDI2-pre TMS PDI2 Compound PDI2 was synthesized following previously published protocols under modified conditions. 2 Briefly, to a two-necked flask containing PDI2-pre (54 mg, 59 µmol) was added 16 ml of methylcyclohexane under Ar atmosphere. A MeH suspension (10 ml) of potassium carbonate (K 2 C 3, 52 mg, 0.38 mmol) was purged with Ar and added into the flask. The biphasic mixture was stirred vigorously for 7 h at 303 K (30 C), after which the product was extracted with CHCl 3. The organic phase was dried over NaS 4, evaporated, and purified by silica gel column chromatography (CHCl 3 ) to yield a red solid. The solid was further purified by reprecipitation from CHCl 3 and MeH to afford a dark red solid (5.8 mg, 13%). 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.87 (m, 6H), (m, 36H), 1.77 (m, 4H), 3.83 (s, 2H), 4.22 (m, 4H), 8.72 (d, J = 8.4 Hz, 2H), 8.86 (s, 2H), (d, J = 8.4 Hz, 2H). 13 C NMR was not obtained owing to the poor solubility. Elemental analysis (calcd for C 52 H 58 N 2 4 : C, 80.59; H, 7.54; N, 3.61): found C, 80.47; H, 7.56; N, S3

5 (2D = 2-octyldodecyl) TMS S N 2D N 2D S TMS DPP2-pre KF THF, H 2 S N 2D N 2D S DPP2 Compound DPP2 was synthesized from DPP2-pre according to the literature procedure. 3 Purple solid (94%); 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.85 (m, 12H), (m, 64H), 1.89 (m, 2H), 3.59 (s, 2H), 3.97 (d, J = 7.7 Hz, 4H), 7.37 (d, J = 4.1 Hz, 2H), 8.82 (d, J = 4.1 Hz, 2H). 13 C NMR (101 MHz, CDCl 3 ): δ (ppm) = 14.27, 14.28, 22.82, 22.85, 26.29, 29.44, 29.51, 29.64, 29.71, 29.79, 29.85, 30.13, 30.14, 31.26, 32.03, 32.08, 37.93, 46.54, 76.40, 85.56, , , , , , , Elemental analysis (calcd for C 58 H 89 N 2 2 S 2 : C, 76.51; H, 9.85; N, 3.08): found C, 76.32; H, 9.60; N, S4

6 S2. NMR Data 1 H NMR (top) and 13 C NMR (bottom) spectra of NDI1-pre in CDCl 3 at 298 K. S5

7 1 H NMR (top) and 13 C NMR (bottom) spectra of NDI1 in CDCl 3 at 298 K. S6

8 1 H NMR (top) and 13 C NMR (bottom) spectra of NDI2 in CDCl 3 at 298 K. S7

9 1 H NMR spectrum of PDI2 in CDCl 3 at 318 K. 13 C NMR was not obtained owing to the poor solubility. S8

10 1 H NMR (top) and 13 C NMR (bottom) spectra of DPP2 in CDCl 3 at 298 K. S9

11 S3. Supporting Data 10 4 ε / M 1 cm 1 8 NDI NDI1 6 NDI Wavelength / nm Figure S1. UV vis spectra of NDI, NDI1, and NDI2 in CH 2 Cl 2 at 298 K. S10

12 Figure S2. 13 C NMR spectrum of NDI1-DIPA in CDCl 3 at 298 K. The peak at around 0 ppm (*) is attributed to tetramethylsilane. S11

13 (a) Exp m/z (b) Sim m/z Figure S3. MALDI TF-MS chart of NDI1-DIPA (positive ion, reflectron mode) and (b) its calculated isotopic distribution (calcd for C 38 H 53 N 3 4 ; [M+H] + ). S12

14 (a) 10 4 ε / M 1 cm NDI NDI + DIPA C 8 H 17 N N C 8 H 17 NDI Wavelength / nm (b) 10 4 ε / M 1 cm NDI1-pre NDI1-pre + DIPA C 8 H 17 N N C 8 H 17 NDI1-pre TMS Wavelength / nm Figure S4. (a) UV vis spectra of NDI in the absence (red line) and presence (dashed blue line) of DIPA (47 mm) in CH 2 Cl 2 at 298 K. (b) UV vis spectra of NDI1-pre in the absence (red line) and presence (dashed blue line) of DIPA (236 mm) in CH 2 Cl 2 at 298 K. S13

15 (a) Absorbance Time / min Wavelength / nm (b) Absorbance at 610 nm ln (k/t) T 1 / K Time / min Figure S5. (a) UV vis spectral changes observed upon addition of DIPA (94.2 mm) to a 1,2-dimethoxyethane solution of NDI1 (60 µm) at 298 K. (b) Time profiles of the absorbance change at 610 nm in the reaction of NDI1 and DIPA at different temperatures (298 K; blue circle, 313 K; green circle, 323 K; orange circle, 333 K; red circle), fitted by pseudo-first-order kinetic curves with R 2 values of over Inset: Eyling plot for the amine adduct (NDI1-DIPA) formation. S14

16 (a) (b) Transmittance (c) Wavenumber / cm Wavenumber / cm 1 Figure S6. Solid-state IR spectra (ATR mode) of (a) a nonvolatile amine (polyethyleneimine, linear) (b) NDI1, and (c) NDI1 and polyethyleneimine after being ground in an agate mortar. The sharp peak of NDI1 at 2097 cm 1, assigned to the C C stretching vibration, completely disappeared upon grinding. This result indicates that the terminal alkyne of NDI1 reacts with the amine quantitatively. S15

17 Abs. (normalized) Wavelength / nm Figure S7. UV vis spectra of spin-coated films of NDI1 (red line), NDI1 exposed to DIPA vapor for 2 h (blue line), and NDI1-DIPA (gray dashed line). The blue line corresponds to the gray dashed line, indicating the quantitative conversion of NDI1 into NDI1-DIPA. S16

18 (a) Absorbance nm (b) Wavelength / nm 1.5 Abs. at 659 nm DIPA + TFA + DIPA + TFA + DIPA + TFA + DIPA + TFA 0 Number of Cycles Figure S8. (a) UV vis spectra of NDI1 (47 µm, dashed black line) upon addition of DIPA (113 mm, blue line), and then TFA (104 mm, red line) in tetrachloroethane at 298 K. (b) Absorption changes at 659 nm upon addition of DIPA and TFA. S17

19 Figure S9. 1 H NMR spectra of (a) NDI2, (b) NDI2-DIPA, and (c) NDI2-(DIPA) 2 in CDCl 3 at 298 K. The olefinic coupling constants of the vinyl protons in NDI2-DIPA and NDI2-(DIPA) 2 are J = 13.6 Hz and 13.8 Hz, respectively. S18

20 Figure S C NMR spectra of (a) NDI2-DIPA and (b) NDI2-(DIPA) 2 in CDCl 3 at 298 K. S19

21 (a) Exp m/z (b) Sim (c) m/z Exp m/z (d) Sim m/z Figure S11. (a) MALDI TF-MS chart of NDI2-DIPA (positive ion, reflectron mode). (b) Its calculated isotopic distribution (calcd for C 40 H 53 N 3 4 ; [M+H] + ). (c) MALDI TF-MS chart of NDI2-(DIPA) 2 (positive ion, reflectron mode). (d) Its calculated isotopic distribution (calcd for C 46 H 68 N 4 4 ; [M+H] + ). S20

22 (a) Absorbance Time / min 0 95 (c) Absorbance Time / min Wavelength / nm Wavelength / nm (b) Absorbance at 624 nm ln (k/t) T 1 / K (d) Absorbance at 675 nm ln (k/t) T 1 / K Time / min Time / min Figure S12. (a) UV vis spectral changes observed upon addition of DIPA (11.8 mm) to a 1,2-dimethoxyethane solution of NDI2 (40 µm) at 333 K. (b) Time profiles of the absorbance change at 624 nm in the reaction of NDI2 and DIPA at different temperatures at 333 K, fitted by a pseudo-first-order kinetic curve with an R 2 value of Inset: Eyling plot for the amine monoadduct formation, NDI2-DIPA. (c) UV vis spectral changes observed upon addition of DIPA (5.89 M) to a 1,2-dimethoxyethane solution of NDI2 (40 µm) at 333 K. (d) Time profiles of the absorbance change at 675 nm in the reaction of NDI2 and DIPA at different temperatures at 333 K, fitted by a pseudo-first-order kinetic curve with an R 2 value of Inset: Eyling plot for the amine bisadduct formation, NDI2-(DIPA) 2. S21

23 (a) (b) 1.41 V 0.96 V 5 µa 1.33 V 1.63 V 5 µa 0.38 V Potential / V (vs. Fc/Fc + ) Figure S13. Cyclic voltammograms (scan rate: 100 mv s 1 ) of (a) NDI2 and (b) NDI2-DIPA in deaerated CH 2 Cl 2 (1 mm) containing 0.1 M TBAPF 6. S22

24 Figure S14. 1 H NMR spectra of (a) PDI2 at 318 K, (b) the monoadduct at 298 K, and (c) the bisadduct of dibutylamine at 298 K in CDCl 3. The olefinic coupling constants of the vinyl protons in the monoadduct and the bisadduct are J = 13.3 Hz and 13.5 Hz, respectively. S23

25 Figure S15. 1 H NMR spectra of (a) DPP2, and (b) the monoadduct of dibutylamine in CDCl 3 at 298 K. The olefinic coupling constant of the vinyl protons in the monoadduct is J = 13.5 Hz. S24

26 Figure S16. 1 H NMR spectra of (a) NDI2, and (b) the monoadduct, and (c) the bisadduct of dibutylamine in CDCl 3 at 298 K. The olefinic coupling constants of the vinyl protons in the monoadduct and the bisadduct are J = 13.6 Hz and 13.7 Hz, respectively. S25

27 Figure S17. 1 H NMR spectra of (a) NDI1, and (b) the monoadduct of dibutylamine in CDCl 3 at 298 K. The olefinic coupling constant of the vinyl protons in the monoadduct is J = 13.6 Hz. S26

28 (a) 1 µa 1.14 V 0.93 V 5 µa Potential / V (vs. Fc/Fc + ) (b) 10 µa 0.64 V 1.48 V 0.53 V Potential / V (vs. Fc/Fc + ) Figure S18. (a) Cyclic voltammogram (scan rate: 100 mv s 1 ) and differential pulse voltammogram of PDI2 (saturated concentration: < 1 mm) in deaerated CH 2 Cl 2 containing 0.1 M TBAPF 6. The concentration of PDI2 was not able to be determined accurately owing to its poor solubility. The integral values of the first and the second reduction peaks of PDI2 are different, presumably because (1) the solubility of PDI2 increases to change the saturated concentration, (2) PDI2 in the neutral state forms an aggregate under the experimental conditions, which results in the unclear reduction processes. 4 (b) Cyclic voltammogram (scan rate: 100 mv s 1 ) of DPP2 (1 mm) in deaerated CH 2 Cl 2 containing 0.1 M TBAPF 6. Because the oxidation process of DPP2 is not reversible, the peak-top values of the oxidation (DPP2/DPP2 + ) and the reduction (DPP2 + /DPP2) waves are shown. S27

29 Table S1. X-ray crystallographic data for NDI2 formula C 34 H 38 N 2 4 formula weight (fw) crystal system space group triclinic P1 _ T / K 213(2) a / Å (2) b / Å (4) c / Å (10) α / deg (2) β / deg (2) γ / deg (2) V / Å (6) Z 2 D c / g cm λ / Å (Mo Κα) µ / mm measured reflections 6509 independent reflections 3813 observed reflections 3130 with I > 2.0σ(I) parameters refined 182 R 1 (I > 2.0σ(I)) wr 2 (all data) GF CCDC S28

30 Table S2. Cartesian coordinates (Å) for the optimized structure of NDI1 in the ground state (total energy: E = hartree) Atom X Y Z N N C C C C C C C C C C C C C C C C H H H H H H C H H C H H C H H C H H C H H C H H C H H C H H H C H H C H H C H H C H H C H H C H H H H C H C S29

31 Table S3. Cartesian coordinates (Å) for the optimized structure of NDI1-DIPA in the ground state (total energy: E = hartree) Atom X Y Z N N C C C C C C C C C C C C C C C C C C H H N H H H H C C H H H H C H H H C H H H C H H H C H H H C H H C H H C H H C H H C H H C H H C H H C H H H C H H C H S30

32 H C H H C H H C H H C H H H H S31

33 S4. References 1 D. Buckland, S. V. Bhosale, S. J. Langford, Tetrahedron Lett. 2011, 52, C. D. Schmidt, N. N. Lang, N. Jux, A. Hirsch, Chem. Eur. J. 2011, 17, W. A. Braunecker, S. D. osterhout, Z. R. wczarczyk, R. E. Larsen, B. W. Larson, D. S. Ginley,. V. Boltalina, S. H. Strauss, N. Kopidakis, D. C. lson, Macromolecules 2013, 46, K. Balakrishnan, A. Datar, T. Naddo, J. Huang, R. itker, M. Yen, J. Zhao, L. Zang, J. Am. Chem. Soc. 2006, 128, 739. S32